Preparation of nondusting organic detergent compositions



Patented Nov. 29, 1949 PREPARATION OF NONDUSTING ORGANIC DETERGENTCOMPOSITIONS Robert Bangs Colgate, Washington, D. (7., Emil EdwardDreger, Summit, and Kenneth Lyman Russell, Nutley, N. J., assignors toColgate- Palmollve-Peet Company, Jersey City, N. J., a

corporation of Delaware No Drawing. Continuation of application SerialNo. 256,720, February 16, 1939. This application August 25, 1943, SerialN.'500,'004

17 Claims.

1 This invention relates to the preparation of nondusting organicdetergents, other than soap, and particularly to the method of preparingnondusting organic compounds, having a non-caror or chips, to form afine dust. It has been found that the formation of such a dust is aserious disadvantage in the marketing of the newer detergents since thefine dust sifts from its package with a consequent loss. Furthermore,because of the small particle size, the dust remains suspended in theair when the detergent is poured from the container, thus causing anunpleasant irritation of the nose and eyes of the housewife or otheruser of the product. In the case of the more inflammable materials, thepossibility of fires or dust explosions is likewise increased. Inaddition, the products are non-uniform in size which causes diflicultyin dispensing and handling in general. When the detergent products aretoo finely divided they tend to cake and form gels with water and theydo not dissolve as readily as beads of the same products. Theseundesirable results have lessened the sales appeal of the dustcontainingproduct.

Furthermore, if the material is formed into grains or similar particles,the proportion of fines is very high and these fines must be screenedfrom the product and reworked. This entails additional expense andcauses further breakdown and dusting of the larger particles during thescreening treatment.

Attempts to overcome this dusting have included the hydration of theorganic detergents, but the results proved to be unsatisfactory. Ifsufiicient water is preesnt to appreciably overcome the dusting of thedetergent material, then the latter will generally be tacky or stickyand .tend to ball or gum up when produced in the forms having at leastone dimension relatively small.

It has now been discovered that normally-dusting, solid organicdetergents having an inorganic acid salt radical in the molecule, whichagents usually do not contain free hydroxy groups in their molecule, canbe sprayed, rolled or extruded to form substantially dry, non-dustingproducts by incorporating in the organic detergents a. hydroxy aliphaticcompound boiling above C. and preferably a polyhydroxy compound of thisIt has been found that the incorporation of such substances, preferablybetween about 1% and about 10% based on total solids content, withorganic detergents such as salts of long-chain alcohol sulphates andalkylated aromatic sulphonic acids having not more than about 3%moisture in the final product, produces a composition which isespecially adapted for economical sheeting on rolls, spray-drying andthe like. The products are more plastic and can be worked readilywithout substantial dusting, crumbling, and formation of fines. Thefinal products are not sticky and possess all the advantages of theoriginal detergent and in some cases improved surface active properties.

The type of compounds which are preferably incorporated with the organicdetergents, either alone or in any desired combination, are hydrophilic,including water-soluble, polyhydric allphatic substances such asglycerol, polyglycerols. glyceroses, glyceramine, chlorhydrins, glycericacid; monoglycerldes of carboxylic acids including the long andshort-chain fatty acids, and naphthenic acids; glycerol mono-sulphatesalts; glycerol monoethers; polyglycerol ethers and esters having atleast two free hydroxy groups; pentantriol 1,2,5 and the monoethers andmonoesters (organic and inorganic) thereof; glycols including ethyleneglycol, pentan-diol 1,2, pentan-diol 1,5, octadecan-diol fromhydrogenated ricinoleic acid, polyethyleneglycols and other polyglycols;aliphatic polyhydric alcohols having more than three hydroxy groups inthe molecule including erythritol, arabitol, mannitol. sorbitol; thewatersoluble aldehyde, ketone, halide, ether, acid and amine derivativesof these alcohols as well as the water-soluble partial esters and ethersthereof including glucose, sorbitol monocaprylate, glucose monoacetate,sucrose, arabinose and fructose; water-soluble gums and starches as wellas their water-soluble esters or ethers including gum arabic,tragacanth; water-soluble cellulose ethers such as methyl and ethylcelluloses; and watersoluble polyvinyl alcohols and water solublepartial ethers and esters thereof.

The organic detergents may be combined with other agents which reducedusting such as mineral oils, fatty oils, long chain aliphaticmonohydric alcohols, cyclohexanol, tetrahydrofurfuryl alcohol, decalinand like agents, but it is preferable that at least one agent of theclass of water-soluble polyhydric aliphatic substances also beincorporated.

The substances, alone or in combination, which can be improved by thispresent method of preventing dusting include salts of the long-chainalkyl primary and secondary sulphates, phosphates and borates, such asthe sodium salt of the dodecyl sulphate; salts of the monosulphate ofglycol monoethers and monocarboxylic acid esters. such as the sodiumsalt of the sulphate oi diethylene glycol monolaurate; salts of aromaticsulphonates including the alkylated derivatives thereof such as thesodium salt of hexyl naphthalene 'sulphonic acid, salts of diphenyl andlong-chain alkylated diphenyl monoand polysulphonic acids, and theneutralized products prepared by the sulphonation of aromatic mineraloil extracts in liquid sulphur dioxide; alkyl sulphonic acid saltsincluding tetradecyl sulphonic acid "sodium salt and aliphatic mineraloil sulphonate salts; salts ofrlong-chain alkyl esters and long-chainalkyl amides of sulpho-acetic acid; the salts of monoethers andmonocarboxylic acid esters of isethionic acid, and the salts ofmonocarboxylic acid amides of taurine. The tendency for these materialsto dust is amplified if they contain inorganic salts, such as sodiumcarbonate, borax, sodium silicate, sodium phosphate or sodium sulphate,the last two salts often being formed in the product during theneutralization.

The following examples indicate some of the advantages obtainable by thepresent invention but they are not intended to limit the scope thereof.

Example I One thousand parts of an aqueous preparation containing 200parts by weight of the sodium salt of sulphated fatty alcohols obtained,by hydrogenation, from coconut oil, and 200 parts by weight of sodiumsulphate are intimately mixed with twenty-five parts by weight of themonoglyceride of coconut oil fatty acids. The mix ture is thenspray-dried, by the method described in U. S. Patent 1,652,900, to forma uniformly granular product having only a small percentage of fines andsubstantially no tendency to dust.

If the same sulphate mixture is similarly treated without the additionof the monoglycerides, a large quantity of fines will be produced whichare hard to collect and which must be sieved from the remainder of theproduct thus reducing the efliciency of the process. In addition theresulting product shows a marked tendency to dust and irritate the noseand eyes of the user.

Example II An aqueous preparation containing 50 parts by weight of thesodium salts of sulphonated, longchain alkylated phenols, 50 partssodium sulphate, parts of borax and 3 parts of glycerol were spray-driedin a tower with hot gases to form a finely divided product having littlefines content. The glycerol prevents the formation of excessivequantities of fines and the product resists dusting.

The borax is added to the aromatic sulphonate material to be spray-driedfor a particular purpose. It has been found that in the spray-drying ofsalts of aromatic sulphonic acids including the alkylated and otherderivatives thereof, there is when associated with the inorganicsulphates which are usually present in these products as a result of theneutralization of the excess of sulphonating agents. This problemappears to be unique with the sulphonated aromatic compounds since it ispossible to spray-dry aliphatic sulphates such as monoslycerldemonosulphates without fire hazard. This is most unusual since thesesulphonates are considerably more stable than the surface activealiphatic sulphates and if flame is applied they will not burn freelyand will not sustain combustion when the flame is removed, whereas thealiphatic sulphates, on the other hand, with or without inorganicsulphates will burn more freely and will, in some instances, sustaincombustion even when the flame is removed.

It is a feature of this invention that the presence of alkaline buildermaterials of the type of borax, trisodium phosphate, and sodiumsilicate, during the spray-drying of salts of aromatic sulphonic acidsas well as alkylated and other derivtives thereof, prevents thesematerials from taking fire and burning during the process.

It is also possible to add polyhydroxy alkyl and/or polyalkyl aminesand/or ammonium bases to the normally dusting organic detergents for thepurpose of preventing such dusting, and in the case of salts of aromaticsulphonic acids these substances serve the additional purpose ofpreventing fires. Triethanolamine, diethanolamine, glycerolamine,diglycerolamine, and triglycerolamine serve very well for this purpose.

Example III To 600 parts by weight of an aqueous preparation containing100 parts of a mixture of 37% sodium sulphate and 63% of the sodium saltof the sulphonic acids produced by sulphonating a refined fraction of aliquid sulphur dioxide extract of a Gulf Coast petroleum with fumingsuiphuric acid while dissolved in liquid sulphur dioxide, there is addedabout 2.0 parts of triethanolamine and 2.0 parts glycerol. The detergentcomposition is dried on heated rolls to a powder with little dusting andsubstantially no gumming.

If the quantities of triethanolamine and glycerine are doubled,practically all dusting is absent.

Example IV Two hundred and seventy-five parts of an aqueous preparationcontaining 2 parts by weight of glycerol, 6 parts by weight 1triethanclamine, and 100 parts by weight of a mixture of about 40%sodium sulphate and about 60% of the sodium salts of the aromaticsulphonic acids produced by sulphonating a liquid sulphur dioxideextract of a Borneo petroleum with fuming sulphuric acid while dissolvedin liquid sulphur dloxide, is spray-dried with heated air in a spraytower without any fire hazard to yield a relatively uniform product withlittle fines content and substantially no tendency to dust.

Example V A preparation containing 500 parts by weight of water, 8 partsby weight of the monoglycerides of coconut oil fatty acids, 100 parts byweight of the mixture of about 37% sodium sulphate and 63% 0f the sodiumsalts of the sulphonic acids prepared by sulphonating a refined fractionof a liquid sulphur dioxide extract of a Gulf Coast petroleum withfuming sulphuric acid while dissolved in liquid sulphur dioxide, isdried on heated rolls with substantially no dusting. a

Even half the quantity of monoglycerides .will likewise reduce theamount of dusting but not to the same extent as the 8% of monoglyceridedoes in the above example.

Although the above examples are all directed to the treatment of .sodiumsalts of the organic detergents and sulphuric acid, it is also withinthe scope of this invention to similarly process other salts includingthose of calcium, magnesium, and other alkaline earth metals; alkalinemetals; earth metals; ammonium and substituted ammonium such asethanolamine, and mono-, diand tri-amyl amine; and pyridinonium andsubstituted pyridinonium.

The fire hazard in spray-drying is particularly troublesome in thespray-drying of salts of sulphonated diphenyl and alkylated (long-chain)derivatives thereof. For example, a mixture of equal parts sodiumsulphate and sodium salts of sulphonated alkylated diphenyls, when anaqueous preparation thereof is sprayed in a spray tower, takes fire,causing injury to the apparatus and destruction of the product. However,a mixture of parts of the sodium salts of sulphonated alkylateddiphenyls, 3 parts of sodium sulphate and 2 parts alkaline soap buildersuch as borax will not burn during the spray-drying of preparationsthereof.

It should be noted that among the substances suggested as being suitableas dust preventing and fire preventing agents there are found manymaterials which serve additional highly desirable functions. Forexample, monoglycerides have super-fatting properties and appear toimprove materially the functions of the organic detergents.

' The alkylol amine compounds are not only effective in the preventionof fires and dusting, but they also serve as wetting and emulsifyingagents. Many of the other materials likewise serve these and/or otherfunctions including flavoring, plasticizing, solubilizing, preserving,anti-spattering, lubricating, water-softening, thickening, humidifying,and the like.

Other agents may be added before, during or after producing the finalproduct, among which are soaps; coloring agents; inert fillers; alkalinesoap builders such as sodium carbonate; ammonia and ammonium salts;organic liquids; perfumes; fats; oils; waxes; gums; resins; germicidesand deodorants; water-softening pyroand hexameta-phosphoric acidcompounds; or any of the common water-soluble alkaline metal salts. Thetype of addition agent which is to be incorporated will depend on thepurposes for which the composition is to be used. The resultingcompositions can be used wherever agents of this type have beenpreviously employed or are likely to be employed such as in thehousehold, as well as in the textile, cosmetic, paper, plastic andleather industries.

This application is a continuation of our prior application Serial No.256,720, filed February 16, 1939 (now abandoned).

While the process herein described is well adapted for carrying out theobjects of the present invention, it is understood that variousmodifications may be made thereof. The invention includes all suchmodifications and changes as come within the scope of the appendedclaims.

We claim:

1. The process of preparing improved detergents which comprisesspray-drying an aqueous carbon atoms.

2. The process of preparing improved an aqueous alkaline preparationcomprising essentially water, a sodium salt of an alkylated arylsulphonic acid and a monoglyceride of a fatty acid having at least sixcarbon atoms.

3. The process of preparing improved detergent compositions whichcomprises spray-drying an aqueous preparation comprising essentiallywater, a water-soluble salt of alkyl aromatic sulphonic acids and asmall proportion of monoglycerides of fatty acids, each fatty acidhaving at least six carbon atoms to the molecule said proportion beingwithin the range of about 1 to 10% based on total solids content.

4. The process of preparing improved detergent compositions whichcomprises spray-drying an aqueous preparation comprising essentiallywater, a normally-dusting water-soluble salt of an alkyl arylsulphonicacid and a monoglyceride of a fatty acid which has at least sixcarbon atoms to the molecule.

5. The process of preparing improved detergent compositions whichcomprises preparing an aqueous mixture comprising essentially water, anormally-dusting water-soluble salt of an aryl sulphonic acid and amonoglyceride of a fatty acid having at least six carbon atoms to themolecule, and converting said mixture to particle form with substantialdrying.

6. The process of preparing improved detergent compositions whichcomprises spray-drying an aqueous preparation comprising essentiallywater, a solid normally-dusting water-soluble salt of an alkylated arylsulphonic acid and a small proportion of an aliphatic polyhydroxycompound which contains only carbon, hydrogen and oxygen, saidproportion being within the range of about 1 to 10% based on totalsolids content.

7. The process of preparing improved detergent compositions whichcomprises preparing an aqueous mixture comprising essentially water, anormally-dusting. solid synthetic organic detergent having anon-carboxylic acid group in the molecule, and an aliphatic polyhydroxycompound which contains only carbon, hydrogen and oxygen, and convertingsaid mixture to particle form with substantial drying to produce aproduct which is substantially dry and which would form a fine dust inthe absence of the aliphatic polyhydroxy compound.

8. The process of claim 7 in which product is formed by spray-drying.

9. The process which comprises spray-drying an aqueous preparationcomprising essentially water, a normally-dusting water-soluble salt of asulphated fatty alcohol and a monoglyceride of a fatty acid containingat least six carbon atoms to the molecule.

10. The process of preparing improved detergents which comprisesspray-drying an aqueous preparation comprising essentially water, themono-glycerides of coconut oil fatty acids and the sodium salts of themixed sulphates of fatty alcohols, derived by hydrogenation from coconutoil.

11. The process of preparing improved detergents Which comprisespreparing an aqueous mixture comprising essentially water, themonoglycerides of coconut oil fatty acids and the sodium salts of themixed sulphates of fatty aldetergent compositions which comprisesspray-drying cohols, derived by hydrogenation from coconut oil, and thenconverting said mixture to particle form with substantial drying.

12. The process of preparing improved detergents and like agents whichcomprises spraydrying an aqueous alkaline preparation comprisingessentially water, a water-soluble salt of an alkylated aryl sulphonicacid and a polyhydroxy aliphatic compound which contains only carbon,hydrogen and oxygen.

13. The process of preparing improved detergents which comprisespreparing an aqueous mixture comprising essentially water, the sodiumsalts of the mixed sulphates of fatty alcohols, derived by hydrogenationfrom the fatty oil, and a monoglyceride of a fatty acid having at leastsix carbon atoms, and then converting the mixture to particle form withsubstantial drying.

14. The process of preparing improved detergents which comprisesspray-drying an aqueous preparation comprising essentially water, anormany-dusting, solid synthetic organic detergent having anon-carboxylic acid group in the molecule, glycerine and a monoglycerideof a fatty acid having at least six carbon atoms.

15. A composition of matter in the form of spray-dried particlescomprising a normallydusting, solid synthetic organic detergent having anon-carboxylic acid group in the molecule, glycerine and a monoglycerideof a fatty acid having at least six carbon atoms, the sum of theglycerine and monoglyceride amounting to about 1 to 10% of the totalsolids content.

16. A composition of matter in particle form having at least one shortdimension comprising a normally-dusting, solid synthetic organicdetergent having a non-carboxylic acid group in 8 the molecule, and analiphatic po yhydroxy compound which contains only carbon, hydrogen andoxygen.

17. .A composition of matter in particle form, having at least one shortdimension comprising a normally-dusting water-soluble salt of an alkylaromatic sulphonicacid and a small proportion] of a monoglyceride of afatty acid having at least six carbon atoms, said proportion beingwithin the range of about 1 to 10% based on total solids content.

ROBERT BANGS COL-GATE. EMIL EDWARD DREGER. KENNETH LYMAN RUSSELL.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,843,316 Daimler Feb. 2, 19321,968,797 Bertsch July 31, 1934 2,175,285 Duncan Oct. 10, 1939 2,179,174Brandt Nov. 7, 1939 2,205,946 Flett June 25, 1940 2,226,075 Rowe Dec.24, 1940 2,298,650 Samaras et a1. Oct. 13, 1942 FOREIGN PATENTS NumberCountry Date 429,088 Great Britain May 28, 1935 477,521 Great BritainDec. 28, 1937 OTHER REFERENCES Emulsions, booklet of Carbide & CarbonChemical Corp, N. Y. (1930) Pa e 5.

